Two-Step Noncatalyzed Hydrolysis Mechanism of Imines at the Air–Water Interface
Xuhong Qian, Fangfang Ma, Deming Xia, Xiaojing Li, Jingwen Chen, Hong‐Bin Xie, Joseph S. Francisco
Abstract
The hydrolysis of imines has long been assumed to be their main atmospheric fate, based on early studies in the field of organic chemistry. However, the hydrolysis mechanism and kinetics of atmospheric imines remain unclear. Here, an advanced Born–Oppenheimer molecular dynamics method was employed to investigate the noncatalyzed hydrolysis mechanism and kinetics at the air–water interface by selecting CH 2 NH as a model molecule. The results indicate that CH 2 NH exhibits a pronounced surface preference. The noncatalyzed hydrolysis of CH 2 NH follows a unique two-step reaction mechanism involving first proton transfer and then OH – transfer through the water bridge at the air–water interface, in contrast to the traditional one-step mechanism. The calculated reaction rate for the rate-determining step is 3.32 × 10 5 s –1, which is 2 orders of magnitude greater than that of the bulk phase. In addition, the involvement of the interfacial electric field further enhances the reaction rate by approximately 3 orders of magnitude. The noncatalyzed hydrolysis rate at both the air–water interface and the bulk phase is higher than that of the possible acid-catalyzed one, clarifying noncatalyzed hydrolysis as the dominant mechanism for CH 2 NH. This study elucidates that the noncatalyzed hydrolysis of atmospheric imines is feasible at the air–water interface and that the revealed unique two-step hydrolysis mechanism has significant implications in atmospheric and water environmental chemistry.